PVT-CELL

11/11/02
Location
12th floor Benedum

Introduction
This experiment is designed to be an investigation into the phase equilibrium behavior of a single
component fluid. The goals of this experiment are to construct various parts of the pressure-
volume and pressure-temperature diagrams for carbon dioxide, understand vapor pressure,
liquid-vapor equilibria, the critical point, the compressibility of a liquid or vapor, and the Gibbs
phase rule. Finally, the basic relationships between pressure, volume, and temperature will be
explored. Your experimental task will be to generate at least one isotherm (subcritical, critical or
supercritical) for CO2 and/or to generate the vapor pressure curve of CO2 through the critical
point, extending to critical isochore data at supercritical temperatures,.

Theory
Phase diagrams are graphical means of representing equilibrium behavior. There are two main
types of phase diagrams commonly encountered for single component systems, which are
pressure vs. temperature (PT) and pressure vs. volume (PV). Each is a two-dimensional
projection of the three-dimensional PVT diagram.

PT diagrams demonstrate phase dependence on pressure and temperature. At a low-temperature

and a high-pressure region, a solid phase occurs. From the solid region, heating at constant
pressure means the fusion (melting) curve will be passed and the liquid region entered.
Alternatively, by decreasing pressure at constant temperature, the sublimation curve is passed
and the vapor region is entered, Figure 1.
Figure 1: Smith, J.M., H. C. Van Ness, and M. M. Abbott. Introduction to Chemical Engineering Thermodynamics.
McGraw-Hill New York 1996. P.

There are two points on the PT curve that are of particular interest. The first of these is the
critical point, located at the end of the vaporization curve. The liquid and vapor phases become
indistinguishable at this point. Beyond the critical point, there is no phase transition; this is
demonstrated by following path “AB” in Figure 1. The other interesting point is the triple point.
At the triple point, all three phases coexist in equilibrium. At pressures or temperatures lower
than the triple point, it is possible to achieve a phase transition directly from the solid to vapor
phase; such a transition is known as sublimation.

Gibbs phase rule is useful in understanding the degrees of freedom for an equilibrium system. :

F=2-π+N-R
Where: N: Number of chemical species
π: Number of phases present
F: Degrees of freedom
R: Restrictions
At the triple point of pure species, F=2-3+1=0, so this relationship holds only at a point, and
pressure, molar volume, and temperature are all fixed when one is constrained to the triple point
of a single component system. When two-phase equilibria is considered, N=1, π=2 and F=1.
Therefore, one must select a temperature to fix the system at its two-phase pressure. Since there
is one degree of freedom, only one variable can be chosen. The result is that the phase
boundaries on the PT diagram are a curve with one independent variable and one dependent
variable.

A general understanding phase equilibrium may be obtained by examining the lines of constant
volume, isochors, on the PT diagram. Data for this type of experiment can be conducted in a
closed, fixed volume apparatus subjected to changes in temperature. It should be noted that when
we refer to volume in equilibrium behavior, we are referring to molar volume, an intrinsic
property. At the beginning of the experiment, the cylinder sample volume is filled with a
specified amount of material in the two-phase region. If it is filled in such a way that the average
molar volume is less than the critical value, as the cylinder is heated the meniscus will all form a
vapor and depart the vaporization curve. If it is filled in such a way that the average molar
volume is too high, the CO2 will all form a liquid during heating and depart the vaporization
curve. If it is filled such that the average molar volume equals the critical volume, the CO2 will
follow the vaporization curve all the way to the critical point and then follow the critical isochor,
which is tangent to the vaporization curve. Alternately, one can determine the amount of a fluid
introduced to the cell, and then adjust the volume of the cell as the temperature is increased,
maintaining the liquid-vapor interface near the middle of the cell until the critical temperature is
attained. Thereafter, in the supercritical region, the volume of the cell would not be changed as
temperature is increased to values greater than the critical temperature.

The physical significance of this is demonstrated if one observes a liquid and gas mixture
passing through the critical point. As it is approached, the meniscus grows hazy and disappears,
but the level does not change. The molar volumes of the two phases converge on the same value.
The result is that as the critical point is reached on a PT diagram, the slopes of constant molar
volume lines diverging from the phase boundary line for both liquids and gases converge on the
slope of the boundary line. At the critical point, since there is really only one phase, the slopes of
these two lines must converge on the same value, the slope of the phase boundary line itself.

Figure 2: Smith, J.M., H. C. Van Ness, and M. M. Abbott. Introduction to Chemical Engineering Thermodynamics.
McGraw-Hill New York 1996. P.

PV diagrams present phase equilibrium information in a slightly different manner. Data for this
type of experiment is obtained in a closed, variable-volume cell subjected to isothermal
compression and/or expansion. Unlike PT diagrams, a horizontal line represents phase transitions
at a given temperature. Isotherms are important guides for interpreting such graphs.

The critical point is at the maxima of the liquid/vapor region boundary curve. Traveling along
TC, the critical isotherm, in figure 3, it can be seen that no phase transition is observed. More
∂P ∂V
interestingly, it can be observed that at the critical point, |T = 0 , or |T = ∞ . A very small
∂V ∂P
pressure gradient causes a huge change in molar volume; this explains the phenomena of critical
opalescence. Critical opalescence is the phenomena whereby a fluid at the critical point exhibits
color. This is because the localized regions of different density have dimensions that are of the
same size as the wavelength of visible light.
 T>Tc

T<Tc

Figure 3: Smith, J.M., H. C. Van Ness, and M. M. Abbott. Introduction to Chemical Engineering Thermodynamics.
McGraw-Hill New York 1996. P.

Objectives
The objectives of this experiment are to use CO2 with the PVT cell to:
1. Construct at least one isotherm, sub-critical (room T), supercritical, or critical on the PV
diagram; or
2. Construct the LV vapor pressure curve through the critical point, and then collect critical
isochor data.
3. In either experiment above, or in a separate experiment, estimate the critical temperature
by observing the CO2 meniscus disappear in the PT experiment, and watch for critical
opalescence.

Tasks
The first task is to create the isotherm lines on the PV diagram by holding the temperature
constant for each run. This is a variable-volume (independent), fixed temperature, variable
pressure (dependent) experiment. The two temperatures to be chosen are either: one below the
critical temperature (room temperature is adequate), one at the critical temperature, and one
above the critical temperature (not greater than 125°F). A combined graph of the two isotherms
will be constructed for the recorded data. Denote the vapor pressure for the subcritical isotherm
and the critical point (evidenced by the inflection point of the isotherm and critical opalescence,
for the critical isotherm. The second task is to collect LV data along the liquid-vapor phase
boundary all the way to the critical point. Single-phase supercritical fluid, isochoric data must
then be collected at temperatures to at least 125°F. The data should be linear and tangent to the
vapor pressure curve at the critical point. This task is performed by generating the vapor pressure
curve to the critical point (adjustments of the cell volume are acceptable to maintain the LV
interface in the middle of the cell). You will have two indications that you are at the critical
point. (1) The LV meniscus will disappear suddenly, and (2) you may observe critical
opalescence. In the supercritical region, keep the volume constant (isochoric conditions) and
increasing the pressure by increasing the temperature.

Equipment Schematic
Description of Equipment
The overall system consists of: a vessel, the pump, the compressor, the temperature bath unit,
and the camera monitor. The pc runs the software designed to operate the unit. The software
package includes a log in which data is recorded by the program at selected time intervals in a
text file. The vessel is a cylinder with a moveable piston. The movement of the piston directly
controls the volume, which in turn varies the pressure as long as the vessel is not in a two-phase
region. The magnetic stirrer is at the end of the piston. A camera, which displays an inverted
picture, is attached to the opposite end. A heating jacket surrounds the vessel and is controlled by
the heating unit. The pump is used to introduce a specific amount of CO2 into the vessel, and the
compressor used to change the inlet pressure of the CO2, or change its state from a gas to a
liquid.

Experimental Procedure

PV Experiment – generation of Isotherms

Your professor will inform you of which isothermal run you will perform, one at T<Tc, one at
T=Tc, or one at T>Tc. The most efficient way to prepare the cylinder for each run is as follows:
1. First vent any pressure in the system by shutting the cylinder of carbon dioxide and then
opening all downstream valves (Be sure to handle the valves on the pump and vessel
carefully due to their delicate connections). This will allow any gas in the compressor,
pump or vessel to be discharged. You may then crack the valve of the CO2 cylinder for
several seconds to replace the air in the system with carbon dioxide. Start the system
software (Thar Designs) located on the desktop. Close the vessel inlet and outlet valves.
2. Make sure the pump volume is high, approximately 150 ml. Please note that the volume
is adjusted by the decrease/increase pressure button in the software. This button does not
directly control pressure but rather the volume. “Increase pressure” corresponds to
“decrease volume”, while “Decrease pressure” corresponds to “increase volume”.
3. Open the valves at the cylinder discharge and the pump inlet and outlet, but keep the inlet
and outlet valves to the vessel closed. This allows CO2 to flow from the cylinder all the
up to, but not into, the high pressure vessel.
4. First allow CO2 under its own pressure (no compressor used) to flow until the pump is
pressurized to the vapor pressure of carbon dioxide (about 700-900 psia; 48-62 bar).
5. It is now desirable to make sure that the system is filled with compressed liquid carbon
dioxide (the system at the vapor pressure of carbon dioxide may have significant amounts
vapor phase carbon dioxide). Charge the pump with additional liquid CO2 from cylinder
by using the compressor. The compressor has been adjusted such that the maximum
pressure that can be realized in about 1700-2500 psia (110-170 bar). Turn the main
house air valve on, which is located on the back wall of the lab, then turn the blue knob
on the compressor to allow the house air to drive the compressor. You will hear single
“whooshes” of air as the compressor drives the liquid carbon dioxide to the pump. Close
the blue knob after each whoosh and check the system pressure. Do not let the pressure
go above 170 bar (although this should not happen because of our regulation of the
compressor, someone may accidentally re-regulate the compressor to a higher pressure).
6. Now, close the valves at the carbon dioxide cylinder discharge and close the “inlet” valve
to the Thar pump to isolate the cylinder from the pump and vessel. Set the cylinder rate
to 15 (fast) for the following adjustments under the vessel tab. Set the vessel volume to 8-
9 ml, which is a few milliliters above the minimum value of which is about 6 milliliters.
(This is due to “dead space” concerns, which you need not to worry about unless the
plunger must be removed. In such a case, the main seal must be changed or if for any
other reason the cylinder must be opened, consult the lab manual and your instructor.)
7. On the pump tab in the program, set the pressure a bar or so above what you want to
pressurize the vessel to; 150-200 bar; 150 bar is a reasonable value. Record the pressure,
volume and temperature of the pump. Let the computer adjust the pressure of the pump,
or simply use the increase/decrease pressure buttons to achieve the desired pressure. Use
a reference or an equation of state to estimate the CO2 density at this condition.)
8. Now open the valve separating the pump from the vessel. The pump pressure will drop
slightly while the vessel pressure rises rapidly. Once these pressure equilibrate, close the
valve between the pump and the vessel.
9. Now decrease the volume (increase pressure) of the pump until you attain 150 bar.
Record the change in pump volume. (This corresponds to the volume of CO2 at room T
and 150 bar that you put into the vessel).
10. Now decreases the volume (increase the pressure) of the vessel until 150 bar is attained at
ambient temperature. Record the volume.
11. Perform a material balance. Did the volume of CO2 displaced from the pump equal the
volume of CO2 in the vessel? They should be equal if the pressure is re-established at the
initial pressure (150 bar) in this example. You can determine the mass of CO2 in the
vessel if you know the density of CO2 at your initial condition. In room 1270, there is an
old PC in the corner that is programmed to provide accurate CO2 density using a multiple
parameter equation of state for CO2. You should use this program to determine the CO2
density at your initial condition (input T in K and P in atm). (Span and Wagner; 1994). A
copy of this reference is next to the PCCC, you may refer to its tables of values if you
like.
12. To display the camera image on the TV monitor, first press the “PROG” button. Then
press the “ACTION” button. This will display a menu of images. Using the arrows on
the remote, select TV and press the “ACTION” button. From this menu, select “LINE”
for the “Input Select”. Finally, press the “ACTION” button twice to leave the
programming screens.
13. Now the temperature must be set and stabilized. Sub-critical can be performed at room T.
The critical temperature for CO2 is 31.0oC. Supercritical runs should be done at 40-50 C.
Pick your run temperatures accordingly. Turn on the power to the heater located to right
of pump, and the heater controls in the vessel tab of the software and set the value of the
desired temperature. As long as your temperature is relatively low (<~45oC) you can turn
the cooling switch “on” on the unit itself to achieve better temperature control. Do not
use cooling with high temperature or else the condenser may be damaged.
14. Once the temperature has stabilized around the desired value, pick a plunger speed. It
should be slow enough so the system may thermally equilibrate; 12 is a good value. In
the data-recording tab, set your software to record all of the possible parameters, which
include the vessel pressure (eg. V pres) , vessel density, vessel temperature, pump
pressure, pump density, and pump temperature. Although we are only concerned with
the vessel data, all the parameters must be selected in order for the software to record the
data correctly. Be sure to save each run to a different data file. Then under the vessel
tab, begin your run by clicking the “on” switch in order to control the volume (not auto).
 Use the camera to note when the system undergoes phase changes. Be sure not to cut
each run short; enough data points are needed for low and high molar volumes.
Specifically, for the sub-critical runs; you need single-phase vapor data, single phase
liquid data and phase change data! (If you are unable to expand the cell enough to reach
the single phase data region; recompress the vessel to a higher pressure and smaller
volume, and then slowly “bleed” CO2 from the vessel through the vessel outlet valve
until the system is all vapor with a tiny liquid phase. Change the vessel volume if
necessary to attain this condition more precisely. Now expand the cell and collect single
phase vapor data. Use the Span equation of state at your lowest pressure value to
determine the “actual” mass of CO2 for this set of vapor phase data.) If you are doing a
critical isotherm run, be sure to note the critical opalescence as you approach the critical
point on the run at the critical temperature. If the Vessel Volume is not an option on the
Data Recording selections, record at least 6 liquid phase data points, 6 phase change
data points, and 6 vapor phase data points “by hand” during the run. Record vessel
volume, vessel T, vessel P and vessel density.
15. If you miss the critical opalescence during your run, complete the critical isotherm data
collection anyway. You can subsequently set your apparatus to the critical conditions of
carbon dioxide; Tc = 304.1K (31C); Pc = 73.8 bar (72.8 atm); Vc = 93.9 cc/mol; critical
mass density = 0.469 gr/cc.
16. Vent the system when you are finished by opening the vent valve of the vessel and the
valve between the pump and the vessel.
17. Repeat steps 1 – 16 for the remaining temperatures as necessary.

PT Experiment
For the PT diagram, you will construct a part of the vaporization curve and the critical
isochor.
1. Refer to steps 1-12 above. Also make sure to record vessel pressure – temperature –
volume and density data. Determine how much CO2 is in the vessel. Do not vent or add CO2
during your experiment.
2. Now expand the vessel volume until the interface is in the middle of the vessel (note: the
density reading on the PC will not be correct for 2-phase conditions because density is
 calculated with an equation of state for single phase systems). The density value is accurate
for single-phase, liquid, vapor or supercritical conditions though.
3. Increase T and read the 2-phase P (vapor pressure). Adjust the vessel volume in an
attempt to keep the interface in the middle.
4. When you reach the critical point, the interface will suddenly disappear and colors may
be observed. DO NOT CHANGE THE VOLUME OF THE SYSTEM ONCE YOU REACH
THE CRITICAL POINT.
5. Increase T and record P thereafter to obtain critical isochor data. Use the Span equation
of state (the PC in the corner of room 1270) to determine the “actual” density of CO2 for your
highest pressure data point.
6. Vent the system when you are finished by opening the vent valve of the vessel (which
vents to the lab air) and the valve between the pump and the vessel.

Data Analysis
You will need to import your data into excel using the fixed width import option. The column
labels the software uses are misaligned and you will need to re-label them appropriately.

For the PV diagram, plot all isotherms on the same diagram. Do not forget to plot pressure as a
function of molar volume (mL/mol) rather than density (g/mL), which the program supplies.

If the Vessel Volume is not an option on the Data Recording selections, record at least 6
liquid phase data points, 6 phase change data points, and 6 vapor phase data points “by
hand” during the run. Record vessel volume, vessel T, vessel P and vessel density.

You should use the vessel T as the T in your plots of the data.
You should use the vessel P as the P in your plots of the data.
There are 2 ways to estimate specific volume for your plots.
1. You should realize that the vessel density values are based on the Peng-Robinson equation of
state; they are not actual measurements of density! Therefore specific volumes based on the
inverse of the vessel density are based on the Peng-Robinson equation of state, T and P.
2. You should use the vessel V as the volume for determining specific volume (vessel volume/gr
of CO2 in the apparatus as determined from the Span equation of state in Step 11). The use of
these values is a more accurate representation of your data!

Label each isotherm with the average temperature value for the run, since the temperature in the
cell does fluctuate a little bit. There is one important glitch in the method that should be obvious
from the subcritical isotherm. The slope of P vs V starts off very steep as one decreases P from
very high liquid-phase values (P drops quickly as V increases slightly), then the data jumps up in
molar volume, then it decays slowly. The density in the program is not the “experimental”
density, but one based on the Peng-Robinson equation of state. Soon after the phase change
begins, the program begins calculating molar volumes that reflect the gaseous phase; these
volumes do not reflect the average value and are not correct until the phase change has ended
and the cell id filled with vapor and a tiny drop of liquid (saturated vapor conditions).

If you do a critical isotherm, identify the critical pressure and volume and calculate your relative
error. You may wish to do this either graphically or by realizing a study on the inflection point.

For the PT diagram, plot pressure as a function of temperature. The critical temperature should
have been observed in the experiment. At supercritical temperatures, the critical isochor should
be linear and tangent to the vapor pressure curve at the critical point. Use a vapor pressure
correlation for CO2 to calculate your relative error for vapor pressure. Use Aspen Plus to
generate a vapor pressure and/or critical isochor, but be careful in your selection of the
thermodynamic model. You may select the Peng-Robinson equation of state.

(The PR EOS gives accurate vapor pressures and vapor volumes/density and is available in
Aspen, but does not give highly accurate liquid volumes. The Span EOS (which is not is Aspen)
is an equation of state valid only for pure CO2 and gives very accurate liquid and vapor
volume/density.)
References

Lyde, David R. CRC Handbook of Chemistry and Physics. Boca Raton: CRC Press, 1993.

Smith, J.M., H. C. Van Ness, and M. M. Abbott. Introduction to Chemical Engineering

Thermodynamics. New York: McGraw-Hill, 1996.

Thar Designs Inc. PEA-30 ml Phase Equilibrium Analyzer Operation Manual. MN-03, 1999.

Span, R. and Wagner, W.; A New Equation of State for CO2 Covering the Fluid Region from
the Triple Point Temperature to 1100 K at Pressures up to 800 MPa; J. Phys. Chem. Ref. Data;
25 (6) 1996; 1509 – 1596.